Bio-derived 1,3-propanediol and its conjugate esters as natural and non irritating solvents for biomass-derived extracts, fragrance concentrates, and oils

ABSTRACT

Compositions containing 1,3-propanediol and an extraction product are provided, and the 1,3-propanediol in the composition is biologically derived. Also provided are processes for extracting an extract from a source. These processes include providing an ester of 1,3-propanediol and mixing the 1,3-propanediol ester with the source. This serves to extract the extract from the source into the ester. The processes also include separating the source from the ester and extract. Also provided are compositions containing an ester of 1,3-propanediol and an extraction product. In these compositions, the ester can have at least 3% biobased carbon.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. ProvisionalApplication Ser. No. 60/772,471, filed Feb. 10, 2006; U.S. ProvisionalApplication No. 60/772,194, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/772,193, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/772,111, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/772,120, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/772,110, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/772,112, filed Feb. 10, 2006, U.S. ProvisionalApplication No. 60/846,948, filed Sep. 25, 2006, U.S. ProvisionalApplication No. 60/853,920, filed Oct. 24, 2006, U.S. ProvisionalApplication No. 60/859,264, filed Nov. 15, 2006, U.S. ProvisionalApplication No. 60/872,705, filed Dec. 4, 2006 and U.S. ProvisionalApplication No. 60/880,824, filed Jan. 17, 2007, the disclosures ofwhich are expressly incorporated herein by reference in theirentireties.

FIELD OF THE INVENTION

The invention relates to compositions comprising solvents and extracts,and methods of extracting compounds from materials using solvents.

BACKGROUND OF THE INVENTION

Consumers and manufacturers are increasingly concerned with theenvironmental impact of all products. The effort towards environmentalimpact awareness is a universal concern, recognized by governmentagencies. The Kyoto Protocol amendment to the United Nations FrameworkConvention on Climate Change (UNFCCC) currently signed by 156 nations isone example of a global effort to favor safer environmentalmanufacturing over cost and efficiency. Especially when applied to goodslike, personal care, cosmetics, therapeutics and cosmeceuticals,consumers are increasingly selective about the origins of the productsthey purchase. The 2004 Co-operative Bank's annual Ethical ConsumerismReport (www.co-operativebank.co.uk) disclosed a 30.3% increase inconsumer spending on ethical retail products (a general classificationfor environmental safe, organic and fair trade goods) between 2003 and2004, while total consumer spending during the same period rose only3.7%.

One of the single greatest environmental concerns to consumers is theglobal warming effect and greenhouse gases that contribute to theeffect. Greenhouse gases are gases that allow sunlight to enter theatmosphere freely. When sunlight strikes the Earth's surface, some of itis reflected back towards space as infrared radiation. Greenhouse gasesabsorb this infrared radiation and trap the heat in the atmosphere. Overtime, the amount of energy sent from the sun to the Earth's surfaceshould be about the same as the amount of energy radiated back intospace, leaving the temperature of the Earth's surface roughly constant.However, increasing the quantity of greenhouse gases above the quantitythat existed before the rise of human industrialization is thought toincrease the retained heat on the Earth's surface and produce the globalwarming observed in the last two centuries.

Carbon dioxide is singled out as the largest component of the collectionof greenhouse gases in the atmosphere. The level of atmospheric carbondioxide has increased 50% in the last two hundred years. Any furtheraddition of carbon dioxide to the atmosphere is thought to further shiftthe effect of greenhouse gases from stabilization of global temperaturesto that of heating. Consumers and environmental protection groups alikehave identified industrial release of carbon into the atmosphere as thesource of carbon causing the greenhouse effect. Only organic productscomposed of carbon molecules from renewably based sources such as plantsugars and starches and ultimately atmospheric carbon are considered tonot further contribute to the greenhouse effect, when compared to thesame organic molecules that are petroleum or fossil fuel based.

In addition to adding carbon dioxide to the atmosphere, current methodsof industrial production of propanediols produce contaminants and wasteproducts that include among them sulfuric acid, hydrochloric acid,hydrofluoric acid, phosphoric acid, tartaric acid, acetic acids, Alkalimetals, alkaline earth metals, transitional metals and heavy metals,including Iron, cobalt, nickel, copper, silver, molybdenum, tungsten,vanadium, chromium, rhodium, palladium, osmium, iridium, rubidium, andplatinum (U.S. Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and 5,10,036).

There is a need for all manufactures to provide products reducedenvironmental impacts, and to especially consider the carbon load on theatmosphere. There is also an environmental advantage for manufacturersto provide products of renewably based sources. Further, there is a needfor a proven solvent which is produced with no or little increase to thepresent carbon-dioxide level in the environment.

Published U.S. Patent Application No. 2005/0069997 discloses a processfor purifying 1,3-propanediol from the fermentation broth of a culturedE. coli that has been bioengineered to synthesize 1,3-propanediol fromsugar. The basic process entails filtration, ion exchange anddistillation of the fermentation broth product stream, preferablyincluding chemical reduction of the product during the distillationprocedure. Also provided are highly purified compositions of1,3-propanediol.

Personal care, animal care, cosmetic, therapeutic, pharmaceutic,nutraceutic, aromatherapy, fragrance and cosmeceutic formulationsbenefit from glycols in the compositions as, for example, surfactants,humectants, solvents, neutralizers, emulsifiers, preservatives and/orfragrance enhancers and fixatives. Typically the glycol component inpersonal care applications include propylene glycol, 1,3-butyleneglycol, or 2-methyl-1,3-propanediol. Because of production costs andrelative low purity, conventional 1,3-propanediol, though exhibitingproperties equal to if not better than the aforementioned glycols,generally is not used in such compositions.

Moreover, in the context of personal care, animal care, cosmetic,therapeutic, pharmaceutic, nutraceutic, aromatherapy, fragrance andcosmeceutic formulations incorporating a botanical, vegetal,protein/peptide, marine, algae or milk extract, or fragrance concentrateor oil, consumers pay attention to the quality and environmental impactof the product. Currently, botanical, vegetal, protein/peptide, marine,algae and milk extracts, and fragrance concentrates utilize chemicalsolvents, such as propylene glycol, 2-methyl-1,3-propanediol, butyleneglycol, dipropylene glycol, synthetic glycerin, and ethanol, for theextraction process. In many cases these chemical solvents are used incombination with each other. Despite the fact these chemicals aresuitable solvents, they have an intrinsic disadvantage because theyrepresent a petroleum-based component of an otherwise “all natural”product. Additionally, safety assessments of these solvents provideevidence that they can cause skin irritation. (Cosmetic IngredientReview Expert Panel (1994) Final Report on the Safety Assessment ofPropylene Glycol and Polypropylene Glycols. J. Am. College Toxicol.,13(6):437-491).

Essential oils extracted from plants are widely used cosmetic andpersonal care formulations. Colors extracted from plants are used in thefood and non-food-industry. Medicinal plant extractions are being usedfor the treatment various disorders. Though several methods can be usedfor extraction of flavors, fragrances, colors, and active ingredients,solvent extraction is one of widely used method. Selective extraction ofrequired ingredients, stability of the extracted ingredients, andseparation of ingredients from unwanted solvents are key factors forextraction. When volatile solvents such as ethanol used for extractionof active ingredients, they need to be removed before using theingredients in formulations. When solvents are removed some of theactive ingredients may not be stable and decompose.

SUMMARY OF THE INVENTION

Compositions comprising 1,3-propanediol and an extraction product areprovided, and the 1,3-propanediol in the composition is biologicallyderived. Also provided are processes for extracting an extract from asource. These processes comprise providing an ester of 1,3-propanedioland mixing the 1,3-propanediol ester with the source. This serves toextract the extract from the source into the ester. The processes alsoinclude separating the source from the ester and extract. Also providedare compositions comprising an ester of 1,3-propanediol and anextraction product. In these compositions, the ester can have at least3% biobased carbon.

DETAILED DESCRIPTION

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Solvents for diluting and extracting natural extracts are oftensynthetic, petroleum based organic solvents. Botanical, vegetal,protein/peptide, marine, algae, and milk extracts, also known as anessential oils, are an attractive component in many compositions. Theseessential oils impart aromatics, active ingredients, and otherfunctionalities such as hand-feel, softening, emoillency, healing,cooling, refreshing, antimicrobial, astringency, nail-strengthening,promotion of healthy skin tissue and hair, cleansing, stimulating,whitening, delivery of anti-oxidants and skin-soothing attributes to aproduct. Essential oils are the volatile oils of plant/vegetal,protein/peptide, lipid, marine, algae or milk materials that have beenremoved either by distillation or solvent extraction.

Biologically-derived 1,3-propanediol and its conjugate esters can beused as a solvent to extract essential oils and other extracts fromextract sources. Bio-derived 1,3-propanediol and its conjugate esterscan be used as a solvent system for botanical extracts and fragranceconcentrates and oils at a 10% to approaching 100% concentration range.

Additionally, biologically-derived 1,3-propanediol and its conjugateesters can be used as a solvent to dilute or solubilize extracts incompositions. Biologically-derived 1,3-propanediol and its conjugateesters are unique as solvents in that they are naturally derived, andtherefore attractive to consumers who avoid synthetic chemicals.

Biologically-derived 1,3-propanediol and its conjugate esters providefor non-irritating solvents for the extraction and dilution ofbotanicals, vegetal, protein/peptide, marine, algae, milk substrates orfragrance concentrates and oils. In an aspect of the invention thesolvent is composed of all natural components, the term “all natural” asused herein refers to a product that is manufactured from ingredientsthat are natural occurring. Specifically, biologically derived1,3-propanediol comprises non-petroleum based carbon.

The conjugate esters of biologically-derived 1,3-propanediol discussedherein include the mono and diesters of biologically derived1,3-propanediol.

Biologically-derived 1,3-propanediol or its ester conjugates areemployed as chemical solvents for extraction or diluent of a botanicalextract or fragrance concentrate or oil. The process of extracting anextract from a source comprises: (a) providing 1,3-propanediol, an esterof 1,3-propanediol, or a mixture thereof; (b) mixing the1,3-propanediol, the ester of 1,3-propanediol, or the mixture thereofwith the source, which extracts the extract from the source into theester; and (c) separating the source from the extract and1,3-propanediol, the ester of 1,3-propanediol, or the mixture thereof.

The process of extraction involves use of a dried substrate such asplant material which is macerated with solvent. Maceration is the mostcommon and economically important technique for extracting aromatics inthe modern perfume industry. In this method, raw materials are submergedin a solvent that can dissolve the desired aromatic or other extractcompounds. Maceration lasts between fractions of an hour to months.Maceration is often used to extract fragrant compounds from woody orfibrous materials, as well as animal sources. This technique is alsouseful to extract odorants that are too volatile for distillation oreasily denatured by heat.

Alternatively the solvent can be percolated though the substratematerial until sufficient soluble materials have leached from thebiomass or substrate. The substrate debris is separated from the extractby straining, filtering, or centrifugation.

Another technique for extracting compounds from a raw material issupercritical fluid extraction. This technique uses low heat to reducedegradation of the extract compounds. Supercritical CO₂ can be used inthis extraction technique.

Extraction can be performed in accordance with the invention by otherextraction techniques as well, including distillation.Biologically-derived 1,3-propanediol and its conjugate esters can beused as solvents in distillation extractions. In this technique,commonly used to obtain aromatic compounds from plants, such as orangeblossoms and roses, the raw material is heated and the fragrantcompounds are recollected through condensation of the distilled vapor.Distillation methods include steam distillation, in which steam is usedto drive out volatile fragrant compounds from plant material, leaving acondensate which is called a hydrosol. Distillation also includes dry ordestructive distillation where the raw material is heated without acarrier solvent. In this case, biologically-derived 1,3-propanediol andits conjugate esters are used as a solvent to dilute the fragrantcompounds after extraction.

In yet another method of extraction, known as expression, raw materialis physically squeezed or compressed and the extruded oils arecollected. This method is known as extraction and is most commonlyperformed to extract compounds from the peels of fruits in the citrusfamily, as these sources contain sufficient oils to make this methodfeasible. Enfleurage is another extraction method appropriate for usewith biologically derived 1,3-propanediol, its conjugate esters, ormixtures thereof.

Biologically derived 1,3-propanediol and its conjugate esters are usefulas a solvents for extractions, and as a component in compositionscomprising botanical extracts. Botanical sources include, but are notlimited to all plants, seeds, stems, roots, flowers, leaves, pollen,spices, and oils. One type of extract appropriate for extraction ordilution is the herbal extract.

An herbal extract is a liquid solution of herbs and solvent. The driedor fresh herbs are combined with solvent, then the solid matter isremoved leaving only the oils of the herbs mixed with the solvent. Thisprocess is called extraction, and the process produces an herbalextract.

Herbal extracts are sold as dietary supplements and alternative medicineand commonly used for flavoring in baking, cooking or in beverages. Theyare also used in personal care products such as skin and hair products.

A small amount of the carbon dioxide in the atmosphere is radioactive.This 14C carbon dioxide is created when nitrogen is struck by anultra-violet light produced neutron, causing the nitrogen to lose aproton and form carbon of molecular weight 14 which is immediatelyoxidized in carbon dioxide. This radioactive isotope represents a smallbut measurable fraction of atmospheric carbon. Atmospheric carbondioxide is cycled by green plants to make organic molecules during theprocess known as photosynthesis. The cycle is completed when the greenplants or other forms of life metabolize the organic molecules producingcarbon dioxide which is released back to the atmosphere. Virtually allforms of life on Earth depend on this green plant production of organicmolecule to produce the chemical energy that facilitates growth andreproduction. Therefore, the 14C that exists in the atmosphere becomespart of all life forms, and their biological products. These renewablybased organic molecules that biodegrade to CO₂ do not contribute toglobal warming as there is no net increase of carbon emitted to theatmosphere. In contrast, fossil fuel based carbon does not have thesignature radiocarbon ratio of atmospheric carbon dioxide.

Assessment of the renewably based carbon in a material can be performedthrough standard test methods. Using radiocarbon and isotope ratio massspectrometry analysis, the biobased content of materials can bedetermined. ASTM International, formally known as the American Societyfor Testing and Materials, has established a standard method forassessing the biobased content of materials. The ASTM method isdesignated ASTM-D6866.

The application of ASTM-D6866 to derive a “biobased content” is built onthe same concepts as radiocarbon dating, but without use of the ageequations. The analysis is performed by deriving a ratio of the amountof radiocarbon (14C) in an unknown sample to that of a modern referencestandard. The ratio is reported as a percentage with the units “pMC”(percent modern carbon). If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount of Biomassmaterial present in the sample.

The modern reference standard used in radiocarbon dating is a NIST(National Institute of Standards and Technology) standard with a knownradiocarbon content equivalent approximately to the year AD 1950. AD1950 was chosen since it represented a time prior to thermo-nuclearweapons testing which introduced large amounts of excess radiocarboninto the atmosphere with each explosion (termed “bomb carbon”). The AD1950 reference represents 100 pMC.

“Bomb carbon” in the atmosphere reached almost twice normal levels in1963 at the peak of testing and prior to the treaty halting the testing.Its distribution within the atmosphere has been approximated since itsappearance, showing values that are greater than 100 pMC for plants andanimals living since AD 1950. It's gradually decreased over time withtoday's value being near 107.5 pMC. This means that a fresh biomassmaterial such as corn could give a radiocarbon signature near 107.5 pMC.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming 107.5pMC represents present day biomass materials and 0 pMC representspetroleum derivatives, the measured pMC value for that material willreflect the proportions of the two component types. A material derived100% from present day soybeans would give a radiocarbon signature near107.5 pMC. If that material was diluted with 50% petroleum derivatives,it would give a radiocarbon signature near 54 pMC.

A biomass content result is derived by assigning 100% equal to 107.5 pMCand 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC willgive an equivalent biobased content result of 93%.

Assessment of the materials described herein were done in accordancewith ASTM-D6866. The mean values quoted in this report encompasses anabsolute range of 6% (plus and minus 3% on either side of the biobasedcontent value) to account for variations in end-component radiocarbonsignatures. It is presumed that all materials are present day or fossilin origin and that the desired result is the amount of biobasedcomponent “present” in the material, not the amount of biobased material“used” in the manufacturing process.

“Substantially purified,” as used by applicants to describe thebiologically-produced 1,3-propanediol produced by the process of theinvention, denotes a composition comprising 1,3-propanediol having atleast one of the following characteristics: 1) an ultraviolet absorptionat 220 nm of less than about 0.200 and at 250 nm of less than about0.075 and at 275 nm of less than about 0.075; or 2) a composition havingL*a*b* “b*” color value of less than about 0.15 and an absorbance at 270nm of less than about 0.075; or 3) a peroxide composition of less thanabout 10 ppm; or 4) a concentration of total organic impurities of lessthan about 400 ppm.

A “b*” value is the spectrophotometrically determined “Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290. Theabbreviation “AMS” refers to accelerator mass spectrometry.

The abbreviation “IRMS” refers to measurements of CO₂ by high precisionstable isotope ratio mass spectrometry.

“Biologically produced” means organic compounds produced by one or morespecies or strains of living organisms, including particularly strainsof bacteria, yeast, fungus and other microbes. “Bio-produced,”“biologically-derived” and “biologically produced” are used synonymouslyherein. Such organic compounds are composed of carbon from atmosphericcarbon dioxide converted to sugars and starches by green plants.

“Biologically-based” means that the organic compound is synthesized frombiologically produced organic components. It is further contemplatedthat the synthesis process disclosed herein is capable of effectivelysynthesizing other monoesters and diesters from bio-produced alcoholsother than 1,3-propanediol; particularly including ethylene glycol,diethylene glycol, triethylene glycol, -, dipropylene diol, tripropylenediol, 2-methyl 1,3-propanediol, neopentyl glycol and bisphenol A.“Bio-based”, and “bio-sourced”; “biologically derived”; and“bio-derived” are used synonymously herein.

“Carbon of atmospheric origin” as used herein refers to carbon atomsfrom carbon dioxide molecules that have recently, in the last fewdecades, been free in the earth's atmosphere. Such carbons in mass areidentifiable by the present of particular radioisotopes as describedherein. “Green carbon”, “atmospheric carbon”, “environmentally friendlycarbon”, “life-cycle carbon”, “non-fossil fuel based carbon”,“non-petroleum based carbon”, “carbon of atmospheric origin”, and“biobased carbon” are used synonymously herein.

“Flavoring agents” are substances added to foods, beverages, cosmetics,pharmaceuticals, or medicines to improve the quality of the taste ifsuch compositions. Oils, such as orange oils are considered flavoringagents.

Compositions in accordance with the invention include a compositioncomprising an ester of 1,3-propanediol and an extraction product. Theesters can be a varying amount of biobased carbon depending on thecompound used in the esterification. Biologically derived1,3-propanediol contains biobased carbon. All three carbon atoms in 1,3propanediol are biobased carbons. If the conjugate esters are formedusing carboxylic acids that contain all biobased carbon, then theresulting esters also contain all biobased carbon. If, however, thecarboxylic acids contain non-biobased carbons, i.e. carbons from afossil fuel source, then the resulting ester will contain a percentageof biobased carbon in proportion to the number of carbons contributedfrom the carboxylic acid compared to the three carbons contributed fromthe biologically-derived 1,3-propanediol.

For example, distearate propanediol contains 39 carbon atoms, 18 fromeach of the stearic acid carbon chains and three from the1,3-propanediol. Accordingly, if the stearic acid is non-biobased, 36carbons out of the total 39 in distearate propanediol are non-biobasedcarbon. The predicted biobased content of distearate propanediol madefrom biologically-derived propanediol, and non-biologically derivedstearic acid is 7.7 percent.

In an analysis performed using the ASTM-D6866 method, propylene glycoldibenzoate (BENZOFLEX (R) 284, Velsicol Chem. Corp. Rosemont, Ill.) wasfound to have 0% bio-based carbon content. The same analysis ofpropanediol dibenzoate, synthesized using biologically-derived1,3-propanediol had 19% bio-based carbon content. The predictedbio-based carbon content propanediol dibenzoate made frombiologically-derived 1,3 propanediol is 17.6%, which is within thestandard deviation of the method.

If the stearic acid in the above example is biobased, the resultingdistearate propanediol would have a biobased content of 100%.Accordingly, the conjugate esters of biologically-derived1,3-propanediol have biobased content values proportional to thebiobased content of the acids used to form the esters. The esterstherefore can have biobased content of at least 3% biobased carbon, atleast 6% biobased carbon, at least 10% biobased carbon, at least 25%biobased carbon, at least 50% biobased carbon, at least 75% biobasedcarbon, and 100% biobased carbon.

The compositions comprising an extract and a conjugate ester of1,3-propanediol can be between about 0.1% and about 5% ester, betweenabout 0.5% and about 25% ester, between about 25% and about 50% ester,between about 50% and about 75% ester, and between about 75% and about99% ester, and between 99% and about 100% ester.

Compositions in accordance with the invention also include compositionscomprising 1,3-propanediol and an extract. The 1,3-propanediol of thesecompositions has at least 95% biobased carbon, or alternatively, the1,3-propanediol has 100% biobased carbon. The compositions comprising anextract and 1,3-propanediol can be between about 0.1% and about 5%1,3-propanediol, between about 0.5% and about 25% 1,3-propanediol,between about 25% and about 50% 1,3-propanediol, between about 50% andabout 75% 1,3-propanediol, and between about 75% and about 99%1,3-propanediol.

Compositions in accordance with the invention also include compositionscomprising both 1,3-propanediol and a conjugate ester of 1,3-propanediolalong with an extract. The 1,3-propanediol of these compositions has atleast 95% biobased carbon, or alternatively, the 1,3-propanediol has100% biobased carbon. The compositions comprising an extract and amixture of 1,3-propanediol and a conjugate ester of 1,3-propanediol canbe between about 0.1% and about 5% mixture, between about 0.5% and about25% mixture, between about 25% and about 50% mixture, between about 50%and about 75% mixture, and between about 75% and about 99% mixture.

A mixture of a glycol and ester can be very effective in extractions,and the mixture can remove more active ingredients than either solventalone. More actives are extracted from plant material using a solventmixture because the esters (especially diesters) are non-polar, whereasglycol components are polar. Accordingly, the lipophilic ingredients caneasily be removed from the plants using the ester glycol mixture. Insome cases the density of an ester can be much higher than the densityof the glycol, and after the maceration process the “cake” (the extractof the ester) can easily solidify and separate from the glycol phase.Additionally, the esters can be volatile compounds and in extractionsthe esters can be easily evaporated to obtain concrete, fragrance oil,absolute, or enfleurage.

The 1,3-propanediol, the conjugate esters of 1,3-propanediol, andmixtures thereof can be effective as solvents and diluents when combinedwith other appropriate solvents, including water.

Biologically-Derived 1,3-propanediol

The present invention relates to compositions comprising a botanical,vegetal, protein/peptide, marine, algae, or milk extract or fragranceconcentrate or oil wherein biologically-derived 1,3-propanediol or itsester conjugate is employed as a chemical solvent for extraction ordiluent of the botanical, vegetal, protein/peptide, marine, algae, ormilk extract or fragrance concentrate or oil. “Biologically-derived”means that the 1,3-propanediol is synthesized by one or more species orstrains of living organisms, including particularly strains of bacteria,yeast, fungus and other microbes. Biologically-derived 1,3-propanedioluseful in shampoo or body wash compositions disclosed herein.

Biologically-derived 1,3-propanediol is collected in a high purity form.Such 1,3-propanediol has at least one of the followingcharacteristics: 1) an ultraviolet absorption at 220 nm of less thanabout 0.200 and at 250 nm of less than about 0.075 and at 275 nm of lessthan about 0.075; or 2) a composition having L*a*b* “b*” color value ofless than about 0.15 and an absorbance at 270 nm of less than about0.075; or 3) a peroxide composition of less than about 10 ppm; or 4) aconcentration of total organic impurities of less than about 400 ppm. A“b*” value is the spectrophotometrically determined Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290.

The level of 1,3-propanediol purity can be characterized in a number ofdifferent ways. For example, measuring the remaining levels ofcontaminating organic impurities is one useful measure.Biologically-derived 1,3-propanediol can have a purity level of lessthan about 400 ppm total organic contaminants; preferably less thanabout 300 ppm; and most preferably less than about 150 ppm. The term ppmtotal organic purity refers to parts per million levels ofcarbon-containing compounds (other than 1,3-propanediol) as measured bygas chromatography.

Biologically-derived 1,3-propanediol can also be characterized using anumber of other parameters, such as ultraviolet light absorbance atvarying wavelengths. The wavelengths 220 nm, 240 nm and 270 nm have beenfound to be useful in determining purity levels of the composition.Biologically-derived 1,3-propanediol can have a purity level wherein theUV absorption at 220 nm is less than about 0.200 and at 240 nm is lessthan about 0.075 and at 270 nm is less than about 0.075.

Biologically-derived 1,3-propanediol can have a b* color value (CIEL*a*b*) of less than about 0.15.

The purity of biologically-derived 1,3-propanediol compositions can alsobe assessed in a meaningful way by measuring levels of peroxide.Biologically-derived 1,3-propanediol can have a concentration ofperoxide of less than about 10 ppm.

It is believed that the aforementioned purity level parameters forbiologically-derived and purified 1,3-propanediol (using methods similaror comparable to those disclosed in U.S. Patent Application No.2005/0069997) distinguishes such compositions from 1,3-propanediolcompositions prepared from chemically purified 1,3-propanediol derivedfrom petroleum sources.

1,3-propanediol produced biologically via fermentation is known,including in U.S. Pat. No. 5,686,276, U.S. Pat. No. 6,358,716, and U.S.Pat. No. 6,136,576, which disclose a process using arecombinantly-engineered bacteria that is able to synthesize1,3-propanediol during fermentation using inexpensive green carbonsources such as glucose or other sugars from plants. These patents arespecifically incorporated herein by reference. Biologically-derived1,3-propanediol can be obtained based upon use of the fermentation brothgenerated by a genetically-engineered Eschericia coli (E. coli), asdisclosed in U.S. Pat. No. 5,686,276. Other single organisms, orcombinations of organisms, may also be used to biologically produce1,3-propanediol, using organisms that have been genetically-engineeredaccording to methods known in the art. “Fermentation” refers to a systemthat catalyzes a reaction between substrate(s) and other nutrients toproduct(s) through use of a biocatalyst. The biocatalysts can be a wholeorganism, an isolated enzyme, or any combination or component thereofthat is enzymatically active. Fermentation systems useful for producingand purifying biologically-derived 1,3-propanediol are disclosed in, forexample, Published U.S. Patent Application No. 2005/0069997 incorporatedherein by reference.

The transformed E. coli DH5α containing cosmid pKP1 containing a portionof the Klebsiella genome encoding the glycerol dehydratase enzyme wasdeposited on 18 Apr. 1995 with the ATCC under the terms of the BudapestTreaty and is identified by the ATCC number ATCC 69789. The transformedE. coli DH5α containing cosmid pKP4 containing a portion of theKlebsiella genome encoding a diol dehydratase enzyme was deposited on 18Apr. 1995 with the ATCC under the terms of the Budapest Treaty and isidentified by the ATCC number ATCC 69790. As used herein, “ATCC” refersto the American Type Culture Collection international depository locatedat 10801 University Boulevard, Manassas, Va., 20110 2209, U.S.A. The“ATCC No.” is the accession number to cultures on deposit with the ATCC.

The biologically derived 1,3-propanediol (bio-PDO) for use in thecurrent invention, produced by the process described herein, containscarbon from the atmosphere incorporated by plants, which compose thefeedstock for the production of bio-PDO. In this way, the bio-PDOcontains only renewable carbon, and not fossil fuel based, or petroleumbased carbon. Therefore the use of bio-PDO and its conjugate esters hasless impact on the environment as the propanediol does not depletediminishing fossil fuels. The use of the use of bio-PDO and itsconjugate esters also does not make a net addition of carbon dioxide tothe atmosphere, and thus does not contribute to greenhouse gasemissions. Thus, the present invention can be characterized as morenatural and having less environmental impact than similar compositionscomprising petroleum based glycols.

Moreover, as the purity of the bio-PDO utilized in the compositions ofthe invention is higher than chemically synthesized PDO and otherglycols, risk of introducing impurities that may cause irritation isreduced by its use over commonly used glycols, such as propylene glycol.

In one embodiment of the invention, a composition comprising1,3-propanediol and an extraction product is provided, where the1,3-propanediol is biologically derived. The biologically-derived1,3-propanediol can have at least 85% biobased carbon, at least 95%biobased carbon, or 100% biobased carbon, when assessed by theapplication of ASTM-D6866 as described above.

A sample of biologically-derived 1,3-propanediol was analyzed using ASTMmethod D 6866-05. The results received from Iowa State Universitydemonstrated that the above sample was 100% bio-based content. In aseparate analysis, also performed using a ASTM-D6866 method, chemical,or petroleum-based 1,3-propanediol (purchased from SHELL) was found tohave 0% bio-based content. Propylene glycol (USP grade from ALDRICH) wasfound to have 0% bio-based content.

It is contemplated herein that other renewably-based orbiologically-derived glycols, such as ethylene glycol or 1,2 propyleneglycol, diethylene glycol, triethylene glycol among others, can be usedin the extractions or compositions of the present invention.

There may be certain instances wherein the extractions or extractcompositions of the invention may comprise a combination of abiologically-derived 1,3-propanediol and one or more nonbiologically-derived glycol components, such as, for example, chemicallysynthesized 1,3-propanediol. In such occasions, it may be difficult, ifnot impossible to determine which percentage of the glycol compositionis biologically-derived, other than by calculating the bio-based carboncontent of the glycol component. In this regard, in the extractionsolvents and extract compositions of the invention, the 1,3-propanediolused as a solvent, or used to form 1,3 propanediol esters, can compriseat least about 1% bio-based carbon content up to 100% bio-based carboncontent, and any percentage there between.

Ester Conjugates of Biologically Derived 1,3-Propanediol

Esters of biologically derived 1,3-propanediol, “bio-PDO” can besynthesized by contacting bio-PDO with an organic acid. The organic acidcan be from any origin, preferably either a biosource or synthesizedfrom a fossil source. Most preferably the organic acid is derived fromnatural sources or bio-derived having formula R₁R₂—COOH. Where in thesubstituent R₁ can be saturated or unsaturated, substituted orunsubstituted, aliphatic or aromatic, linear or branched hydrocarbonhaving chain length 1 to 40 or their salts or alkyl esters. Where in thesubstituent R₂ can be H or COOH. The hydrocarbon chain can also have oneor more functional groups such as alkene, amide, amine, carbonyl,carboxylic acid, halide, hydroxyl groups. Naturally occurring organicacids produced esters containing all biobased carbon. These naturallyoccurring organic acids, especially those produced by a biologicalorganism, are classified as bio-produced and the resulting ester ordiester could thereby also be classified as bio-produced. Naturallyoccurring sources of such fatty acids include coconut oil, variousanimal tallows, lanolin, fish oil, beeswax, palm oil, peanut oil, oliveoil, cottonseed oil, soybean oil, corn oil, rape seed oil. Conventionalfractionation and/or hydrolysis techniques can be used if necessary toobtain the fatty acids from such materials.

Appropriate carboxylic acids for producing esters ofbiologically-derived 1,3-propanediol generally include: (1) C1-C3 carboncontaining mono carboxylic acids, including formic acid and acetic acid;(2) fatty acids, such as those acids containing four or more carbonatoms; (3) saturated fatty acids, such as butyric acid, caproic acid,valeric acid, caprylic acid, capric acid, lauric acid, myristic acid,palmitic acid, stearic acid, arachidic acid, and behenic acid; (4)unsaturated fatty acids, such as oleic acid, linoleic acid, and euricicacid; (5) polyunsaturated fatty acids, such as alpha-linolenic acid,stearidonic acid (or moroctic acid), eicosatetraenoic acid, omega-6fatty acids, arachidonic acids, and omega-3 fatty acids,eicosapentaenoic acid (or timnodonic acid), dosocapentaenoic acid (orclupanodonic acid), and docosahexaenoic acid (or cervonic acid); (6)hydroxy fatty acids, such as 2-hydroxy linoleic acid, and recinoleicacid; phenylalkanoic fatty acids, such as 11-phenyl undecanoic acid,13-phenyl tridecanoid acid, and 15-phenyl tridecanoid acid; and (7)cyclohexyl fatty acids, such as 11-cyclohexyl undecanoic acid, and13-cyclohexyl tridecanoic acid.

The following acids and their salts or alkyl esters are specificallyuseful, acetic, butyric, lauric, myristic, palmitic, stearic, arachidic,adipic, benzoic, caprylic, maleic, palmitic, sebacic, archidonic,erucic, palmitoleic, pentadecanoic, heptadecanoic, nondecanoic,octadectetraenoic, eicosatetraenoic, eicosapentaenoic, docasapentaenoic,tetracosapentaenoic, tetrahexaenoic, docosahexenoic, (alpha)-linolenic,docosahexaenoic, eicosapentaenoic, linoleic, arachidonic, oleic, erucic,formic, propionic, valeric, caproic, capric, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, tartaric, citric,salicylic, acetyl-salicylic, pelargonic, behenic, cerotic, margaric,montanic, melissic, lacceroic, ceromelissic, geddic, ceroplasticundecylenic, ricinoleic, and elaeostearic acid as well as mixtures ofsuch acids. A more preferred list of suitable organic acids are acetic,adipic, benzoic, maleic, sebacic, and mixtures of such acids. A morepreferred list of suitable “fatty acids” meaning generally acids namedcontaining 8-40 carbon in the carbon useful in the present inventioninclude butyric, valeric, caproic, caprylic, pelargonic, capric, lauric,myristic, palmitic, stearic, arachidic, behenic, cerotic, oleic,linoleic, linolenic, margaric, montanic, melissic, lacceroic,ceromelissic, geddic, ceroplastic and the mixtures of such acids. Amongthose acids, these acids, and their salts and alkyl esters are mostpreferred stearic, lauric, palmetic, oleic, 2-ethyl hexanoic, and12-hydroxystearic and mixtures of such acids.

The esters produced include all the appropriate conjugate mono anddiesters of 1,3 propanediol using the described organic acids. Someesters in particular that are produced include propanediol distearateand monostearate, propandiol dilaurate and monolaurate, propanedioldioleate and monooleate, propanediol divalerate and monovalerate,propanediol dicaprylate and monocaprylate, propanediol dimyristate andmonomyristate, propanediol dipalmitate and monopalmitate, propanedioldibehenate and monobehenate, propanediol adipate, propanediol maleate,propanediol dibenzoate, propanediol diacetate, and all mixtures thereof.

In particular, the esters produced include: propanediol distearate andmonostearate, propanediol dioleate and monooleate, propanedioldicaprylate and monocaprylate, propanediol dimyristate andmonomyristate, and all mixtures thereof.

Generally 1,3-propanediol can be contacted, preferably in the presenceof an inert gas reacted with a fatty acid or mixture of fatty acids orsalts of fatty acids in the absence or presence of a catalyst or mixtureof two or more catalysts, at temperatures ranging from 25° C. to 400° C.

During the contacting, water is formed and can be removed in the inertgas stream or under vacuum to drive the reaction complete. Any volatilebyproducts can be removed similarly. When the reaction is complete, theheating can be stopped and cooled.

The catalyst can be removed preferably by dissolving and removing indeionized water. If catalyst can be removed by treating with deionizedwater, the reaction mixture is treated with aqueous solutions of acid orbase to forms salts and removing the salts either by washing orfiltering.

Further purification to obtain high purity fatty esters, preferably forpharmaceutical application can be carried out by dissolving in a solventthat dissolves fatty ester easily at higher temperatures and least atlower temperatures and recrystallizing with or without addition ofadditional solvent at low temperatures.

The catalyst can be an acid for non-limiting examples, sulfuric acid, orp-toluene sulfonic acid. The catalyst can also be a base, fornon-limiting example, sodium hydroxide. The catalyst can also be a salt,for non-limiting example, potassium acetate. The catalyst can also be analkoxide, for non-limiting example, titanium tetraisopropoxide. Thecatalyst can also be a heterogeneous catalyst, for non-limitingexamples: zeolite, heteropolyacid, amberlyst, or ion exchange resin. Thecatalyst can also be a metal salt, for non-limiting examples, tinchloride, or copper chloride, The catalyst can also be an enzyme, suchas those known in the art. The catalyst can also be an organic acid, fora non-limiting example, formic acid. Finally the catalyst can also be anorganometallic compound, for non-limiting example, n-butylstannoic acid.

This process can be carried out in the presence or absence of a solvent.If a solvent is not necessary to facilitate the production of fattyester, it is preferred that the process is carried out in the absence ofsolvent.

The process can be carried out at atmospheric pressure or under vacuumor under pressurized conditions.

Where R₁ and R₂ is a hydrocarbon, preferably with a carbon chain lengthof about 1 to about 40. Such hydrocarbons can be saturated orunsaturated, substituted or unsubstituted, linear or branched

M is hydrogen, an alkali metal or an alkyl group.

Where R₁ is a hydrocarbon, preferably with a carbon chain length ofabout 1 to about 40. Such hydrocarbons can be saturated or unsaturated,substituted or unsubstituted, linear or branched. M is hydrogen, analkali metal or an alkyl group.

Compositions in accordance with the invention comprise esters in whichR1 has one or more functional groups selected from the group consistingof alkene, amide, amine, carbonyl, carboxylic acid, halide, hydroxylgroups, ether, alkyl ether, sulfate and ethersulfate. The esters canhave the formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2, wherein both R1 andR2 are linear or branched carbon chains of a length between about 1 anabout 40 carbons. R1 and R2 can have one or more functional groupsselected from the group consisting of alkene, amide, amine, carbonyl,carboxylic acid, halide, hydroxyl groups, ether, alkyl ether, sulfateand ethersulfate. Additionally, R1 and R2 can be the same carbon chainin the case of a diester.

Any molar ratio of diol to dicarboxylic acid or its salt or its estercan be used. The preferred range of the diol to dicarboxylic acid isfrom about 1:3 to about 2:1. This ratio can be adjusted to shift thefavor of the reaction from monoester production to diester production.Generally, to favor the production of diesters slightly more than abouta 1:2 ratio is used; whereas to favor the production of monoesters abouta 1:1 ratio is used. In general, if the diester product is desired overthe monoester the ratio of diol to dicarboxylic acid can range fromabout 1.01:2 to about 1.1:2; however if the monoester is desired a rangeof ratios from about 1.01:1 to about 2:1 is used.

The catalyst content for the reaction can be from 1 ppm to 60 wt % ofthe reaction mixture, preferably from 10 ppm to 10 wt %, more preferablyfrom 50 ppm to 2 wt % of the reaction mixture.

The product may contain diesters, monoesters or combination diesters andmonoesters and small percentage of unreacted acid and diol depending onthe reaction conditions. Unreacted diol can be removed by washing withdeionized water. Unreacted acid can be removed by washing with deionizedwater or aqueous solutions having base or during recrystallization.

Any ester of 1,3-propanediol can be made or used in accordance with thepresent invention. Short, middle and long chain monoesters and diestersof the 1,3-propanediol can be made. Specifically those acids containingbetween about 1 and about 36 carbons in the alkyl chain can be produced.More specifically, the following monoesters and diesters can beproduced: propanediol distearate (monostearate and the mixture),propandiol dilaurate (monolaurate and the mixture), propanediol dioleate(monooleate and the mixture), propanediol divalerate (monovalerate andthe mixture), propanediol dicaprylate (monocaprylate and the mixture),propanediol dimyristate (monomyristate and the mixture), propanedioldipalmitate (monopalmitate and the mixture), propanediol dibehenate(monobehenate and the mixture), propanediol adipate, propanediolmaleate, propanediol dibenzoate, and propanediol diacetate.

For compositions comprising an extract and 1,3-propanediol, theconjugate esters of 1,3-propanediol, or mixtures thereof, the extractcan be a compound or group of compounds that are extracted from a sourcematerial. In some applications, the extract is extracted from a naturalsource, such as a botanical source. Examples of appropriate naturalextracts include botanical extracts, vegetal extracts, protein extracts,lipid extracts, marine extracts, algae extracts, and milk extracts.

Botanical sources for extracts include the following list of families ofplants and trees: Acanthaceae, Aceraceae, Achariaceae, Achatocarpaceae,Acoraceae, Actinidiaceae, Actiniopteridaceae, Adiantaceae, Adoxaceae,Aegicerataceae, Aetoxicaceae, Agavaceae, Agdestidaceae, Aitoniaceae,Aizoaceae, Akaniaceae, Alangiaceae, Alismataceae, Alliaceae,Alseuosmiaceae, Alstroemeriaceae, Altingiaceae, Alzateaceae,Amaranthaceae, Amaryllidaceae, Amborellaceae, Ampelidaceae,Anacardiaceae, Anarthriaceae, Ancistrocladaceae, Androstachydaceae,Anemiaceae, Angiopteridaceae, Anisophylleaceae, Annonaceae,Anthericaceae, Antoniaceae, Aphyllanthaceae, Apiaceae, Apocynaceae,Aponogetonaceae, Apostasiaceae, Aquifoliaceae, Araceae, Araliaceae,Araucariaceae, Arecaceae, Aristolochiaceae, Asclepiadaceae,Asparagaceae, Asphodelaceae, Aspidiaceae, Aspleniaceae, Asteliaceae,Asteraceae, Asteranthaceae, Asteranthaceae, Asteranthaceae,Asteranthaceae, Aucubaceae, Austrobaileyaceae, Avicenniaceae,Azollaceae, Balanopaceae, Balanophoraceae, Balsaminaceae, Bambuseae,Barringtoniaceae, Basellaceae, Bataceae, Begoniaceae, Berberidaceae,Betulaceae, Bignoniaceae, Bischofiaceae, Bixaceae, Blechnaceae,Bombacaceae, Bonnetiaceae, Boraginaceae, Botrychiaceae, Brassicaceae,Bruniaceae, Brunoniaceae, Buddlejaceae, Burmanniaceae, Burseraceae,Butomaceae, Buxaceae, Byblidaceae, Byttneriaceae, Cabombaceae,Cactaceae, Caesalpiniaceae, Callitrichaceae, Calycanthaceae,Calyceraceae, Campanulaceae, Canellaceae, Cannabidaceae, Cannaceae,Canotiaceae, Capparidaceae, Caprifoliaceae, Cardiopteridaceae,Caricaceae, Carlemanniaceae, Caryocaraceae, Caryophyllaceae,Casuarinaceae, Cayceraceae, Cecropiaceae, Celastraceae,Centrolepidaceae, Cephalotaceae, Cephalotaxaceae, Ceratophyllaceae,Cercidiphyllaceae, Cheiropleuriaceae, Chenopodiaceae, Chloanthaceae,Chloranthaceae, Christenseniaceae, Chrysobalanaceae, Cistaceae,Clethraceae, Clusiaceae, Cneoraceae, Cochlospermaceae, Columelliaceae,Combretaceae, Commelinaceae, Compositae, Connaraceae, Conocephalaceae,Convolvulaceae, Coriariaceae, Cornaceae, Corynocarpaceae, Costaceae,Crassulaceae, Crossosomataceae, Crypteroniaceae, Cryptogram maceae,Cucurbitaceae, Culcitaceae, Cunoniaceae, Cupressaceae, Cyanastraceae,Cyatheaceae, Cycadaceae, Cyclanthaceae, Cyclocheilaceae, Cymodoceaceae,Cynomoriaceae, Cyperaceae, Cypripediaceae, Cyrillaceae, Danaeaceae,Daphniphyllaceae, Datiscaceae, Davalliaceae, Davidsoniaceae,Degeneriaceae, Dennstaedtiaceae, Dialypetalanthaceae, Diapensiaceae,Dichapetalaceae, Dicksoniaceae, Dicrastylidaceae, Didiereaceae,Didymelaceae, Diegodendraceae, Dilleniaceae, Dioscoreaceae, Dipsacaceae,Dipteridaceae, Dipterocarpaceae, Dracaenaceae, Droseraceae,Dryopteridaceae, Dysphaniaceae, Dysphaniaceae, Ebenaceae,Ecdeiocoleaceae, Elaeagnaceae, Elaeocarpaceae, Elaphoglossaceae,Elatinaceae, Empetraceae, Epacridaceae, Ephedraceae, Equisetaceae,Ericaceae, Eriocaulaceae, Erythropalaceae, Erythroxylaceae,Escalloniaceae, Eucommiaceae, Eucryphiaceae, Euphorbiaceae,Eupomatiaceae, Eupteleaceae, Fabaceae, Fagaceae, Flacourtiaceae,Flagellariaceae, Fouquieriaceae, Frankeniaceae, Fumariaceae, Garryaceae,Geissolomataceae, Gentianaceae, Geosiridaceae, Geraniaceae,Gesneriaceae, Ginkgoaceae, Gleicheniaceae, Globulariaceae, Gnetaceae,Goetzeaceae, Gomortegaceae, Goodeniaceae, Goupiaceae, Gramineae,Grammitaceae, Grammitidaceae, Grubbiaceae, Gunneraceae, Guttiferae,Gyrostemonaceae, Haemodoraceae, Haloragaceae, Haloragidaceae,Hamamelidaceae, Heliconiaceae, Helminthostachyaceae, Hemionitidaceae,Hernandiaceae, Heteropyxidaceae, Himantandraceae, Hippocastanaceae,Hippocrateaceae, Hippuridaceae, Hoplestigmataceae, Hostaceae,Humiriaceae, Hydnoraceae, Hydrangeaceae, Hydrocharitaceae,Hydrocotylaceae, Hydrophyllaceae, Hydrostachyaceae, Hymenophyllaceae,Hymenophyllopsidaceae, Hypericaceae, Hypolepidaceae, Hypoxidaceae,Icacinaceae, Idiospermaceae, Illiciaceae, Iridaceae, Isoetaceae,Ixonanthaceae, Juglandaceae, Julianiaceae, Juncaceae, luncaginaceae,Koeberliniaceae, Krameriaceae, Labiatae, Lacistemataceae, Lactoridaceae,Lamiaceae, Lardizabalaceae, Lauraceae, Lecythidaceae, Leeaceae,Leguminosae, Leitneriaceae, Lemnaceae, Lennoaceae, Lentibulariaceae,Lilaeaceae, Liliaceae, Limnanthaceae, Limnocharitaceae, Linaceae,Lindsaeaceae, Lissocarpaceae, Loasaceae, Lobeliaceae, Loganiaceae,Lomariopsidaceae, Lophosoriaceae, Loranthaceae, Lowiaceae,Loxogrammaceae, Loxsomaceae, Lunulariaceae, Luzuriagaceae,Lycopodiaceae, Lygodiaceae, Lythraceae, Magnoliaceae, Malesherbiaceae,Malpighiaceae, Malvaceae, Marantaceae, Marattiaceae, Marcgraviaceae,Marchantiaceae, Marsileaceae, Martyniaceae, Matoniaceae, Mayacaceae,Medusagynaceae, Medusandraceae, Melastomataceae, Meliaceae,Melianthaceae, Menispermaceae, Menyanthaceae, Metaxyaceae, Mimosaceae,Misodendraceae, Monimiaceae, Moraceae, Moraceae, Moringaceae, Musaceae,Myoporaceae, Myricaceae, Myristicaceae, Myrothamnaceae, Myrsinaceae,Myrtaceae, Najadaceae, Negripteridaceae, Nelumbonaceae, Nepenthaceae,Nephrolepidaceae, Nolanaceae, Nyctaginaceae, Nymphaeaceae, Nyssaceae,Ochnaceae, Octoknemaceae, Olacaceae, Oleaceae, Oleandraceae, Oliniaceae,Onagraceae, Oncothecaceae, Onocleaceae, Ophioglossaceae, Opiliaceae,Orchidaceae, Orobanchaceae, Osmundaceae, Oxalidaceae, Paeoniaceae,Pandaceae, Pandanaceae, Papaveraceae, Parkeriaceae, Passifloraceae,Pedaliaceae, Penaeaceae, Pentaphragmataceae, Pentaphylacaceae,Peperomiaceae, Peraceae, Peranemaceae, Periplocaceae, Petrosaviaceae,Philesiaceae, Philydraceae, Phormiaceae, Phrymaceae, Phytolaccaceae,Pinaceae, Piperaceae, Pittosporaceae, Plagiogyriaceae, Plantaginaceae,Platanaceae, Platyzomataceae, Plumbaginaceae, Poaceae, Podocarpaceae,Podophyllaceae, Podostemaceae, Polemoniaceae, Polygalaceae,Polygonaceae, Polypodiaceae, Pontederiaceae, Portulacaceae, Potaliaceae,Potamogetonaceae, Primulaceae, Proteaceae, Psilotaceae, Pteridaceae,Punicaceae, Pyrolaceae, Quiinaceae, Rafflesiaceae, Ranunculaceae,Rapateaceae, Rebouliaceae, Resedaceae, Restionaceae, Rhamnaceae,Rhizophoraceae, Rhoipteleaceae, Rhoipteleaceae, Rhopalocarpaceae,Roridulaceae, Rosaceae, Rubiaceae, Ruscaceae, Rutaceae, Sabiaceae,Saccifoliaceae, Salicaceae, Salvadoraceae, Salviniaceae, Santalaceae,Sapindaceae, Sapotaceae, Sarcolaenaceae, Sarcospermataceae,Sarraceniaceae, Saururaceae, Saxifragaceae, Scheuchzeriaceae,Schisandraceae, Schizaeaceae, Scrophulariaceae, Scyphostegiaceae,Scytopetalaceae, Selaginaceae, Selaginellaceae, Simaroubaceae,Sinopteridaceae, Smilacaceae, Solanaceae, Sonneratiaceae, Sparganiaceae,Sphaerosepalaceae, Sphenostemonaceae, Stachyuraceae, Stackhousiaceae,Staphyleaceae, Stemonaceae, Sterculiaceae, Strasburgeriaceae,Strelitziaceae, Stromatopteridaceae, Strychnaceae, Styracaceae,Symplocaceae, Taccaceae, Taenitidaceae, Tamaricaceae, Taxaceae,Taxodiaceae, Tecophilaeaceae, Tepuianthaceae, Tetracentraceae,Tetragoniaceae, Tetrameristaceae, Theaceae, Theligonaceae,Thelypteridaceae, Theophrastaceae, Thunbergiaceae, Thurniaceae,Thymelaeaceae, Thyrsopteridaceae, Tichodendraceae, Tiliaceae,Tmesipteridaceae, Tovariaceae, Trapaceae, Tremandraceae, Trigoniaceae,Trilliaceae, Triuridaceae, Trochodendraceae, Tropaeolaceae, Turneraceae,Typhaceae, Uapacaceae, Ulmaceae, Urticaceae, Vacciniaceae, Vahliaceae,Valerianaceae, Velloziaceae, Verbenaceae, Violaceae, Vitaceae,Vittariaceae, Vivianiaceae, Vochysiaceae, Welwitschiaceae, Winteraceae,Xanthorrhoeaceae, Xyridaceae, Zamiaceae, Zingiberaceae, Zosteraceae,Zygophyllaceae.

Preferred families of plants and trees include Anacardiaceae Araceae,Balanopaceae, Balsaminaceae, Begoniaceae, Boraginaceae, Buxaceae,Caricaceae, Cucurbitaceae, Clusiaceae, Daphniphyllaceae, Ericaceae,Euphorbiaceae, Fabaceae, Fagaceae, Hippocastanaceae, Hostaceae,Hydrangeaceae, Labiateae, Lilaeaceae, Magnoliaceae, Moringaceae,Myristicaceae, Myrtaceae, Oleaceae, Orchidaceae, Peperomiaceae,Pinaceae, Primulaceae, and Rutaceae.

The preferred species of plants and trees for extract sources includeAchillea millefolium, Aesculus chinensis, Allium sativum, Artemisiaapiacea, Astrocaryum murumuru, Bactris gasipaes, Benincasa hispida,Celastrus paniculatus, Cetraria islandica, Chenopodium quinoa, Cinchonasuccirubra, Citrus bergamia, Citrus sinensis, Coriandrum sativum, Codiumtomentosum, Commiphora molmol, Crataegus cuneata, Cucumis sativus,Eucalyptus globulus, Gleditsia sinensis, Gnetum amazonicum, Hibiscusrosa-sinensis, Jasminum officinale, Lonicera caprifolium, Lonicerajaponica, Lycopersicon esculentum, Malus pumila, Matricaria recutita,Maximiliana maripa, Melaleuca hypericifolia, Melaphis chinensis, Menthapiperita, Mouriri apiranga, Nasturtium officinale, Nelumbo nucifera,Oenothera biennis, Ophiopogon japonicus, Persea americana, Paffiapaniculata, Phellodendron amurense, Phyllanthus emblica, Pisum sativum,Potentilla erecta, Pterocarpus santalinus, Rehmannia chinensis, Resedaluteola, Ribes nigrum, Rosa centifolia, Rubus thunbergii, Spondiasamara, Styrax benzoin, and Thymus vulgaris.

Extract sources also include algae. Families of algae used as extractsources include Acrochaeticaceae, Characeae, Codiaceae, Fucaceae,Laminariaceae, Lemaneaceae, Ulvaceae, and Pamariaceae. Preferred algaespecies include Lemanea fluviatilis (red algea), (L.), Ascophyllumnodosum (brown alga), Lemanea fluviatilis, Lemanea fucina (red algea),Ulva lactuca (green alga), Laminaria digitata, Laminaria ochroleuca.

Extract sources also include members of the kingdom of Fungi. Forextraction, classes of Homobasidiomycetes (or true mushrooms) can beused. Some exemplary mushrooms families include: Meripilaceae,Tricholomataceae, and Ganodermataceae (maitake, shiitake, reishimushrooms). Specific species include: Agaricus bisporus, Agaricuscampestris, Flammulina velutipes Hypsizygus tessulatus, Lentinus edodes,Phellinus linteus, Pleurotus cornucopiae, Pleurotus ostreatus, Tremellafuciformis, Sparassis crispa, Tuber magnatum, and Volvariella volvacea.

Species from the division of Bryophyta, Kingdom of plantae (whichincludes mosses) can be used as extract sources, and some species oflichen can also be used for extraction.

Marine sources, such as plants, algae, plankton, and fish, are used toproduce extracts. Protein and lipid extract sources include plant,animal, fish and human (e.g. Placenta) materials. Milk can be used as anextract source to isolate and concentrate proteins, peptides, andlipids.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of the present disclosurehave been described in terms of preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and methods and in the steps or in the sequence ofsteps of the method described herein without departing from the concept,spirit, and scope of the invention. More specifically, it will beapparent that certain agents which are chemically related may besubstituted for the agents described herein while the same or similarresults would be achieved. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope, and concept of the invention as defined by theappended claims.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

All ingredients used in the preparation of the personal carecompositions described in the following Examples are availablecommercially unless otherwise noted.

The meaning of abbreviations used is as follows “% wt.” means percent byweight; “qs” means as much as suffices; “EDTA” means ethylenediaminetetraacetate; “° C.” means degrees Centigrade; “° F.” is degreesFahrenheit, “Bio-PDO” means biologically-derived 1,3-propanediol; “ppm”is parts per million; “AU” is absorbance unit; “nm” is nanometer(s);“GC” is gas chromatograph; “APHA” is American Public Health Association;“cps” is centipoise; “f/t” is freeze/thaw; “mPa·s” is milliPascalseconds; “D.I.” is deionized.

General Methods:

Standard recombinant DNA and molecular cloning techniques used in theExamples are well known in the art and are described by Sambrook, J.,Fritsch, E. F. and Maniatis, T., Molecular Cloning: A Laboratory Manual,Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 1989, byT. J. Silhavy, M. L. Bennan, and L. W. Enquist, Experiments with GeneFusions, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y., 1984,and by Ausubel, F. M. et al., Current Protocols in Molecular Biology,Greene Publishing Assoc. and Wiley-Interscience, N.Y., 1987.

Materials and methods suitable for the maintenance and growth ofbacterial cultures are also well known in the art. Techniques suitablefor use in the following Examples may be found in Manual of Methods forGeneral Bacteriology, Phillipp Gerhardt, R. G. E. Murray, Ralph N.Costilow, Eugene W. Nester, Willis A. Wood, Noel R. Krieg and G. BriggsPhillips, eds., American Society for Microbiology, Washington, D.C.,1994, or by Thomas D. Brock in Biotechnology: A Textbook of IndustrialMicrobiology, Second Edition, Sinauer Associates, Inc., Sunderland,Mass. 1989.

All reagents, restriction enzymes and materials used for the growth andmaintenance of bacterial cells were obtained from Aldrich Chemicals(Milwaukee, Wis.), BD Diagnostic Systems (Sparks, Md.), LifeTechnologies (Rockville, Md.), or Sigma Chemical Company (St. Louis,Mo.), unless otherwise specified.

Glycerol used in the production of 1,3-propanediol was obtained from J.T. Baker Glycerin USP grade, Lot 325608 and G19657.

Differential Scanning Calorimetry: DSC thermograms were recorded usingUniversal V3 1A TA instrument under constant stream of nitrogen with aheating and cooling rate of 10° C./min.

NMR: 1H NMR spectra were recorded on Bruker DRX 500 using XWINNMRversion 3.5 software. Data was acquired using a 90 degree pulse (p1) anda 30 second recycle delay (d1). Samples were dissolved in deuteratedchloroform and nondeuterated chloroform was used as internal standard.

Isolation and Identification Bio-PDO

The conversion of glycerol to bio-PDO was monitored by HPLC. Analyseswere performed using standard techniques and materials available to oneof skill in the art of chromatography. One suitable method utilized aWaters Maxima 820 HPLC system using UV (210 nm) and RI detection.Samples were injected onto a Shodex SH-1011 column (8 mm×300 mm,purchased from Waters, Milford, Mass.) equipped with a Shodex SH-1011Pprecolumn (6 mm×50 mm), temperature controlled at 50° C., using 0.01 NH2SO4 as mobile phase at a flow rate of 0.5 mL/min. When quantitativeanalysis was desired, samples were prepared with a known amount oftrimethylacetic acid as external standard. Typically, the retentiontimes of glycerol (RI detection), 1,3-propanediol (RI detection), andtrimethylacetic acid (UV and RI detection) were 20.67 min, 26.08 min,and 35.03 min, respectively.

Production of bio-PDO was confirmed by GC/MS. Analyses were performedusing standard techniques and materials available to one of skill in theart of GC/MS. One suitable method utilized a Hewlett Packard 5890 SeriesII gas chromatograph coupled to a Hewlett Packard 5971 Series massselective detector (EI) and a HP-INNOWax column (30 m length, 0.25 mmi.d., 0.25 micron film thickness). The retention time and mass spectrumof 1,3-propanediol generated from glycerol were compared to that ofauthentic 1,3-propanediol (m/e: 57, 58).

Production of Bio-Based Monoesters and Diesters from Bio-Produced1,3-propanediol.

Monoesters and diester of bio-produced 1,3-propandiol may be produced bycombining bioPDO with organic acid. The combination is to be preformedin dry conditions under heat and prolong agitation with a selectedcatalyst. The ratio of monoester to diester produced will vary accordingto the molar ratio of acid to bioPDO and the selection of catalyst.

The production of esters was confirmed using ¹H nuclear magneticresonance. Analyses were performed using standard techniques andmaterials available to one of skill in the art of ¹H NMR.

Proton Nuclear Magnetic Resonance (¹H NMR) Spectroscopy is a powerfulmethod used in the determination of the structure of unknown organiccompounds. It provides information concerning: the number of differenttypes of hydrogens present in the molecule, the electronic environmentof the different types of hydrogens and the number of hydrogen“neighbor” a hydrogen has.

The hydrogens bound to carbons attached to electron withdrawing groupstend to resonate at higher frequencies from TMS, tetramethylsilane, acommon NMR standard. The position of where a particular hydrogen atomresonates relative to TMS is called its chemical shift (δ). Typicalchemicals shifts of fatty ester are as follows.

δ=0.88 for terminal CH₃

δ=1.26, 1.61 and 1.97 for methylene groups of (—CH₂—CH ₂—CH₂), (CH₂—CH₂—C═O) and (O—CH₂—CH ₂—CH₂—O) respectively,

δ=2.28 for methylene group adjustcent to ester (CH ₂—C═O)

δ=4.15 for ester (C(═O)—O—CH ₂—).

Proton NMR can distinguish the protons corresponding to the end groups(CH ₂—OH) (δ=3.7) from that of the middle ester groups (CH ₂—O—C(═O)—)(δ=4.15 and 4.24 for diester and monoester, respectively) and thus it ispossible to identify ester and can monitor the reaction by comparing theintegral areas of these two peaks.

${\%\mspace{14mu}{Esterification}} = \frac{{Combined}\mspace{14mu}{areas}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 41.5\mspace{14mu}{and}\mspace{14mu} 4.24 \times 100}{{{Combined}\mspace{14mu}{areas}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 3.70},{41.5\mspace{14mu}{and}\mspace{14mu} 4.24}}$

Example 1 Conversion of D-glucose to 1,3-Propanediol Under FermentationConditions

E. coli strain ECL707, containing the K. pneumoniae dha regulon cosmidspKP1 or pKP2, the K. pneumoniae pdu operon pKP4, or the Supercos vectoralone, is grown in a 5 L Applikon fermenter for the production of1,3-propanediol from glucose.

The medium used contains 50-100 mM potassium phosphate buffer, pH 7.5,40 mM (NH4)2SO4, 0.1% (w/v) yeast extract, 10 μM CoCl2, 6.5 μM CuCl2,100 μM FeCl3, 18 μM FeSO4, 5 μM H3BO3, 50 μM MnCl2, 0.1 μM Na2MoO4, 25μM ZnCl2, 0.82 mM MgSO4, 0.9 mM CaCl2, and 10-20 g/L glucose. Additionalglucose is fed, with residual glucose maintained in excess. Temperatureis controlled at 37° C. and pH controlled at 7.5 with 5N KOH or NaOH.Appropriate antibiotics are included for plasmid maintenance. Foranaerobic fermentations, 0.1 vvm nitrogen is sparged through thereactor; when the dO setpoint was 5%, 1 vvm air is sparged through thereactor and the medium is supplemented with vitamin B12.

Titers of 1,3-propanediol (g/L) range from 8.1 to 10.9. Yields ofbio-PDO (g/g) range from 4% to 17%.

Example 2 Purification of Biosourced 1,3-Propanediol

Published U.S. Patent Application No. 2005/0069997 discloses a processfor purifying 1,3-propanediol from the fermentation broth of a culturedE. coli that has been bioengineered to synthesize 1,3-propanediol fromsugar. The basic process entails filtration, ion exchange anddistillation of the fermentation broth product stream, preferablyincluding chemical reduction of the product during the distillationprocedure.

1,3-Propanediol, produced as recited in Example 1, was purified, by amultistep process including broth clarification, rotary evaporation,anion exchange and multiple distillation of the supernatant.

At the end of the fermentation, the broth was clarified using acombination of centrifugation and membrane filtration for cellseparation, followed by ultrafiltration through a 1000 MW membrane. Theclarified broth processed in a large rotary evaporator. Approximately 46pounds of feed material (21,000 grams) were processed to a concentratedsyrup. A 60 ml portion of syrup was placed in the still pot of a 1″diameter distillation column. Distillation was conducted at a vacuum of25 inches of mercury. A reflux ratio of approximately 1 was usedthroughout the distillation. Several distillate cuts were taken, thecentral of which received further processing. The material was dilutedwith an equal volume of water, the material was loaded onto an anionexchange column (mixed bed, 80 grams of NM-60 resin), which had beenwater-washed. Water was pumped at a rate of 2 ml/min, with fractionsbeing collected every 9 minutes. Odd number fractions were analyzed, andfractions 3 through 9 contained 3 G. The fractions containing 3 G werecollected and subjected to microdistillation to recover several grams ofpure 1,3-propanediol monomer (which was polymerized to mono and diestersaccording the methods described in Example 2-8).

Example 3 Production of Propanediol Distearate Using P-toluenesulfonicAcid as Catalyst

To prepare propanediol distearate from biosource 1,3-propanediol andstearic acid, biosource 1,3-propanediol was purified using methods as inexamples 1 and 2. 2.58 g (0.033 moles) of biosource 1,3-propanediol,19.45 g (0.065 moles) of stearic acid (Aldrich, 95%), and 0.2125 g(0.001 moles) of p-toluenesulfonic acid (Aldrich 98.5%) were chargedinto glass reactor fitted with mechanical stirrer and the reactor wasflushed with dry nitrogen gas to remove air and moisture for 15 min.Then reaction temperature was raised to 100° C. while thoroughlystirring the reaction mixture under nitrogen flow and continued for 210min.

After completion of the reaction, reaction mixture was cooled to about35° C. and the product was transferred into a beaker. The product waspurified by adding 100 mL of water and thoroughly stirring at 45-60° C.,to form an emulsion for 15 min. The mixture was cooled and the solidpropanediol distearate was separated by filtration.

The product was characterized by ¹H NMR (Nuclear Magnetic Resonance)spectra (CDCl₃ (deuterated chloroform)): δ=0.88 (t, CH ₃—CH₂, 6H), 1.26(t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂-4H) and DSC(Tm=66.4° C. and Tc=54.7° C.).

Example 4 Purity Characterizations of Biologically-Derived1,3-Propanediol

In Table 1 below, biologically-derived 1,3-propanediol (produced andpurified as described in Published U.S. Patent Application No.2005/0069997) (“Bio-PDO”) is compared, in several purity aspects, to twoseparate commercially-obtained preparations of chemically-produced1,3-propanediol (Source A and B).

TABLE 1 Units Source A Source B Bio-PDO Total Org Impurities ppm 570 69580 UV Abs 220 nm, AU 0.25 1.15 0.12 UV Abs 250 nm, AU 0.123 0.427 0.017UV Abs 275 nm AU 0.068 0.151 0.036 UV Abs 350 nm AU 0.013 0.007 0.001Peroxides ppm 67 43 2 CIE L*a*b* ASTM D6290 b* 0.411 0.03 0.1 Carbonylsppm 147 175 1

A typical profile of purity aspects are provided in Table 2 below, on asample of biologically-produced 1,3-propanediol purified by a processdisclosed in Published U.S. Patent Application No. 2005/0069997.

TABLE 2 Units 1,3-Propanediol GC area % 99.992 pH, neat pH 8.22 UV Abs.@ 270 nm, 1:5 dilution AU 0.01 Color APHA 3 Color (Process Measurement)L*a*b* b* 0.10 Water ppm 115 UV abs 220 nm neat AU 0.144 UV abs 250 nmneat AU 0.017 UV abs 275 nm neat AU 0.036 UV abs 350 nm neat AU 0.001Peroxide ppm 2 Metals ppm <1 Sulfur ppm <1 Carbonyl ppm 1

The unit ppm of total organic impurities means parts per million oftotal organic compounds in the final preparation, other than1,3-propanediol, as measured by a gas chromatograph with a flameionization detector. Results are reported by peak area. A flameionization detector is insensitive to water, so the total impurity isthe sum of all non 1,3-propanediol organic peaks (area %) ratioed to thesum of all area % (1,3-propanediol included). The term “organicmaterials” refers to the contaminants containing carbon.

The tables show that the disclosed method of purification provides forhighly pure biologically derived 1,3-propanediol, as compared tocommercially-obtained preparations of chemically-produced1,3-propanediol.

Example 5 Skin Irritation and Sensitization Characterization ofBiologically-Derived 1,3-Propanediol

In a human skin patch test with approximately 100 subjects, 5, 25, and50% PDO did not cause any skin reactions indicative of irritation orsensitization. A second human skin patch test did not produce anyclinically significant dermal irritation or sensitization reactions withconcentrations of 25, 50, and 75% PDO at pH 7, or 75% PDO at pH 4 and 9.Based on these studies PDO is not expected to be a skin irritant orsensitizer in humans. In the second human skin patch test, propyleneglycol (1,2-propanediol or PG) was also tested at 25, 50, and 75% (pH 7)and all three concentrations of PG were patch test irritants andcumulative irritants for human skin.

Examples 6-8 are prophetic and are based on a descriptions from:D'Amelio, Frank S Sr.; Botanicals: A Phytocosmetic Desk Reference; CRCPress 1999, pg. 299-304.

Example 6

A Natural, High Foaming, Gentle Shampoo for Everyday Use PercentSequence Raw Material INCI Name 1.00  1 Deionized Water Water 0.00  1Saponins Saponins 0.00  1 Cocamidopropyl Betaine Cocamidopropyl Betaine.00 1 Cocamide DEA 1:1 Cocamide DEA .10 1 Horsetail Extract, 5:1 BIO-PDOHorsetail Extract .10 1 Comfrey Leaf Extract, 5:1 BIO-PDO Comfrey LeafExtract .10 1 Rosemary Extract, 5:1 BIO-PDO Rosemary Extract .10 1Chamomile Extract, 5:1 BIO-PDO Matricaria Extract .s. 2 50% Aq. SodiumHydroxide Sodium Hydroxide .50 3 Aculyn 22 Thickener¹Acrylates/Steareth-20 Methacrylate Copolymer 5.00  4 Plantaren 2000²Decyl Polyglucose .10 Lipovol A³ Avacado Oil .s. 5 25% Aqueous CitricAcid Citric Acid 0.00  6 UCARE Polymer LR 30M (1.3%)⁴ Polyquaternium-10.00 7 Lipamide MEAA⁴ Acetamide MEA Note: 5:1 Bio-PDO is defined as 5parts biologically derived 1,3-propanediol with 1 part dehydratedbotanical. (20% of a 1:1 extract) ¹Rohm & Haas ²Henkel

Procedure:

-   -   1. Combine Sequence 1 ingredients at room temperature using a        slow to moderate mixing to prevent aeration until homogeneous.    -   2. Adjust pH to 9.2 with Sequence 2 ingredient.    -   3. Slowly add Sequence 3 and continue mixing until polymer is        completely dispersed.    -   4. Add Sequence 4 ingredients slowly and mix until homogeneous.    -   5. Adjust pH to 5.5 with Sequence 5 ingredient.    -   6. Add Sequence 6 slowly and mix until homogeneous.        -   Add Sequence 7 slowly and mix until homogeneous.

Example 7

All Natural Blooming Bath Oil Percent Sequence Raw Material INCI Name15.96  1 Lipovol ALM⁵ Sweet Almond Oil 63.54  1 Lipovol SES¹ Sesame Oil5.00 1 Lipolan R¹ Lanolin Oil 5.00 1 Lipopeg 2-DL PEG-4 Dilaurate 10.00 1 Lipocol 0–2¹ Oleth-2 0.10 1 Propylparaben Propylparaben 0.10 1 VitaminE USP-FCC⁶ Vitamin E 0.10 2 Arnica 5:1 BIO-PDO Arnica Extract 0.10 2Chamomile 5:1 BIO-PDO Chamomile Extract 0.10 2 Comfrey 5:1 BIO-PDOComfrey Extract q.s. 3 D & C Green #6 D & C Green #6 (0.5% Sol'n inBIO-PDO) Note: 5:1 Bio-PDO is defined as 5 parts biologically derived1,3-propanediol with 1 part dehydrated botanical. (20% of a 1:1 extract)³Lipo Chemicals, Inc. ⁴Amerchol ⁵Lipo Chemicals, Inc.

Procedure:

-   -   1. Combine Sequence 1 ingredients under vigorous mixing and heat        to 557° C. until propylparaben is completely dissolved. Cool to        30° C.    -   2. At 30° C., add Sequence 2 ingredients to batch and cool to        25° C.        -   At 25° C., add Sequence 3 until desired shade is obtained.

Example 8

High Humectant, Aqueous Spray-On Moisturizer Percent Sequence RawMaterial INCI Name 92.70  1 Deionized Water Water 2.00 1 Lipocare HA/EC⁷Echinacin 5.00 1 Liponic EG-1¹ Glycereth - 26 0.10 1 Slippery Elm Bark5:1 BIO- Slippery Elm PDO⁸ Extract 0.10 1 Chamomile Extract 5:1 BIO-Matricaria Extract PDO² 0.10 1 Wild Alum Extract 5:1 BIO- CranesbillExtract PDO² Note: 5:1 Bio-PDO is defined as 5 parts biologicallyderived 1,3-propanediol with 1 part dehydrated botanical. (20% of a 1:1extract) ⁶Roche Vitamins and Fine Chemicals ⁷Lipo Chemicals, Inc.⁸BioBotanica/Lipo Chemicals, Inc.

Procedure:

Combine ingredients under vigorous mixing at room temperature untilbatch is clear and uniform.

Example 9 Extraction of Chamomile Flower Powder by Bio-PDO and Bio-PDOEster Mixture

Esters based on biologically-derived 1,3-propanediol were synthesized,purified and characterized as it is described in U.S. Provisional Patentapplication 60/772,112, filed Feb. 10, 2006, incorporated herein byreference.

Biologically-derived 1,3-propanediol and 1,3-propanediol conjugate esterwere used for the extraction of Chamomile flower powder (Martricariarecutita from Egypt, distributor—Mountain Rose Herbs, Oreg.).

The Chamomile powder was mixed with 1,3-propanediol and macerated for 30minutes on a shaking table, then 1,3-propanediol ester was added to themixture and the temperature was raised to 90° C. and the maceration wascontinued for additional 2 hours. The material was filtered through a0.2 μm GHP membrane and the filtrate was analyzed by LC/MS and shown tocontain extracted compounds.

Example 10 Extraction of Chamomile Flower Powder by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of Chamomile flower powder (Mountain RoseHerbs, Oreg.).

The Chamomile powder was mixed with the ester and macerated for 2, 4, 6hours on a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS (UV/VisSpectrophotometer, Varian (Australia), Model: Cary 5000) and the spectrademonstrated that the efficacy of the extracted compounds wasproportional with the time used for the maceration.

Example 11 Extraction of Red Roses by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of dried Red Roses (Rosa centifolia,Mountain Rose Herbs, Oreg.).

The dried roses was mixed with the ester and macerated for 2, 4, 6 hourson a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS.

Example 12 Extraction of Seaweed by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of dried seaweed (local farmers' market).

The dried seaweed was mixed with the ester and macerated for 2, 4, 6hours on a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS

Example 13 Botanical Extraction Using Bio-PDO/Methanol Mixture

Procedure: 5 g of dried Jasmine flower (Jasminum officinale, MountainRose Herbs, Oreg.) was immersed in the mixture of Bio-PDO/methanol(70%:30%) and macerated for 24 h. The material was filtered through a0.2 μm GHP membrane and the filtrate was analyzed by LC/MS. The LC/MSspectra demonstrated the effective extraction of the active ingredients.

Example 14 Honeysuckle Flower Extraction Using Bio-PDO/Deionized WaterMixture

Procedure: 5 g of dried Honeysuckle flower (Lonicera japonica, originChina, distributor Mountain Rose Herbs, Oreg.) was immersed in themixture of Bio-PDO/d.water(50%:50%) and macerated for 24 h. The materialwas filtered through a 0.2 μm GHP membrane and the filtrate was analyzedby LC/MS. The LC/MS spectra demonstrated the effective extraction of theactive ingredients.

Example 15 Eucalyptus Leaf Extraction Using Bio-PDO/Deionized WaterMixture

Procedure: 5 g of dried Eucalyptus leaf (Eucalyptus globulus, originFrance, distributor Mountain Rose Herbs, Oreg.) was immersed in themixture of Bio-PDO/d.water(50%: 50%) and macerated for 24 h. Thematerial was filtered through a 0.2 μm GHP membrane and the filtrate wasanalyzed by LC/MS. The LC/MS spectra demonstrated the effectiveextraction of the active ingredients.

Example 16 Sandalwood Red Powder Extraction Using Bio-PDO/DeionizedWater Mixture

Procedure: 5 g of dried Sandalwood Red Powder (Pterocarpus santalinus,origin Africa, distributor Mountain Rose Herbs, Oreg.) was immersed inthe mixture of Bio-PDO/d.water(50%:50%) and macerated for 24 h. Thematerial was filtered through a 0.2 μm GHP membrane and the filtrate wasanalyzed by LC/MS. The LC/MS spectra demonstrated the effectiveextraction of the active ingredients.

Comparative Example 1 Comparison Between Biologically Derived1,3-propanediol and Propylene Glycol in Plant Material Extractions

Bio-1,3-propanediol and propylene glycol were used to extractingredients from Jasmine flower, Chamomile flower powder (Matricariarecutita) myrrh gum cut benzoin gum powder, and bees wax. LC-MS andGC-MS were used to analyze the extracted ingredients. Qualitativeanalysis confirmed that ingredients extracted using 1,3-propanediol aresame as those extracted using propylene glycol. Additionally,ingredients extracted using bio-1,3-propanediol and mixtures ofbio-1,3-propanediol and methanol were the same.

The major ingredients of chamomile extraction are bisabolol oxide,en-in-dicyclo ether, and Apigenin glucoside. Comparative yields of theseactive ingredients using 1,3-propanediol and propylene glycol(1,2-Propanediol, Aldrich) are shown below in Table 1:

TABLE 1 Bio-1,3-propanediol Propylene Glycol % Extract Product Area Areadifference Bisabolol oxide 9217821^(a) 8760424^(a) 5.2 Apigeninglucoside 3972525^(b) 3549734^(b) 11.2 en-in-dicyclo ethers 9394370^(b)7261956^(b) 29.2 ^(a)GC-MS analysis, ^(b)LC-MS analysis

The table shows the GC-MS/LC-MS peak areas of the extracted ingredientsusing 1,3-propanediol and propylene glycol. Using Bio-1,3-propanediolthe extraction process extracted 29.4 wt % higher en-in-cycloethers,11.2 wt % higher apigenin glucoside, and 5.2 wt % higher bisabolol oxideas compared to the extraction using propylene glycol.

Comparative Example 2

Chamomile flower powder (5 g) was mixed with 50 g of solvent mixture(Bio-PDO/Deionized Water, ratio 1:1, and also the mixture of1,2-Propanediol(Propylene glycol, Aldrich)/Deionized Water, ratio 1:1).The mixture was kept for agitation for 24 h. The extract was filteredand analyzed.

TABLE 2 Comparison of extraction of Chamomile using Bio-PDO andPropylene glycol Bio-PDO/ Propylene glycol/ Product Water Area WaterArea % Difference Bisabolol oxide 25176422 14409166 75 Apigenin 2374215556691 326 Apigenin glucoside 658824 420412 57 en-in-dicyclo ethers1842764 866635 113

The data in Table 2. show the GC-MS/LC-MS peak areas of the extractedingredients using Bio-PDO/water and propylene glycol/water mixtures.Using Bio-PDO/water mixture 75 wt % higher Bisabolol oxide, 326 wt %higher Apigenin, 113 wt % higher en-in-cycloethers, 57 wt % higherapigenin glucoside were extracted than those extracted using propyleneglycol.

Comparative Example 3

Chamomile flower powder (Mountain Rose Herb, Oreg.) (5 g) was mixed with50 g of Bio-PDO also 5 g of Chamomile flower powder was mixed withDeionized Water. The mixture was macerated for 24 h. The extract wasfiltered and analyzed by LC/MS.

TABLE 3 Comparison of extraction of Chamomile using Bio-PDO and WaterProduct Bio-PDO/Area H₂O/Area % Difference Apigenin 63.32 125.53 −50.4Apigenin glucoside 134.58 0 en-in-dicyclo ethers 1340.74 0

Using deionized water apigenin glucoside and en-in-dicyclo ethers werenot extracted though apigenin extraction was higher compared to thatusing Bio-PDO.

1. A composition comprising an ester of 1,3-propanediol and anextraction product, wherein the composition is biodegradable, whereinthe ester is a monomer and comprises at least 3% biobased carbon, andwherein said composition has a lower anthropogenic CO₂ emission profileas compared to a biodegradable composition comprising an ester of1,3-propanediol with a bio-based carbon content of 0%.
 2. Thecomposition of claim 1, wherein the ester has at least 6% biobasedcarbon.
 3. The composition of claim 1, wherein the ester has at least10% biobased carbon.
 4. The composition of claim 1, wherein the esterhas at least 25% biobased carbon.
 5. The composition of claim 1, whereinthe ester has at least 50% biobased carbon.
 6. The composition of claim1, wherein the ester has at least 75% biobased carbon.
 7. Thecomposition of claim 1, wherein the ester has 100% biobased carbon. 8.The composition of claim 1, wherein the ester has the formulaR1-C(═O)—O—CH2-CH2-CH2-OH, wherein R1 is a linear or branched carbonchain of a length between about 1 and about 40 carbons.
 9. Thecomposition of claim 8, wherein R1 has one or more functional groupsselected from the group consisting of alkene, amide, amine, carbonyl,carboxylic acid, halide, hydroxyl groups, ether, alkyl ether, sulfateand ethersulfate.
 10. The composition of claim 1, wherein the ester hasthe formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2, wherein R1 and R2 arelinear or branched carbon chains of a length between about 1 and about40 carbons.
 11. The composition of claim 10, wherein R1 and R2 have oneor more functional groups selected from the group consisting of alkene,amide, amine, carbonyl, carboxylic acid, halide, hydroxyl groups, ether,alkyl ether, sulfate and ethersulfate.
 12. The composition of claim 10,wherein R1 and R2 are the same carbon chain.
 13. The composition ofclaim 1, wherein the ester is selected from the group consisting of: i.propanediol distearate, monostearate and a mixture thereof; ii.propandiol dilaurate, monolaurate and a mixture thereof; iii.propanediol dioleate, monooleate and a mixture thereof; iv. propanedioldivalerate, monovalerate and a mixture thereof; v. propanedioldicaprylate, monocaprylate and a mixture thereof; vi. propanedioldimyristate, monomyristate and a mixture thereof; vii. propanedioldipalmitate, monopalmitate and a mixture thereof; viii. propanedioldibehenate, monobehenate and a mixture thereof; ix. propanediol adipate;x. propanediol maleate; xi. propanediol dibenzoate; xii. propanedioldiacetate; and xiii. mixtures thereof.
 14. The composition of claim 13,wherein the ester is selected from the group consisting of: a.propanediol distearate, monostearate and a mixture thereof; b.propanediol dioleate, monooleate and a mixture thereof; c. propanedioldicaprylate, monocaprylate and a mixture thereof; d. propanedioldimyristate, monomyristate and a mixture thereof; and e. mixturesthereof.
 15. The composition of claim 1, wherein the extraction productis a natural extract.
 16. The composition of claim 15, wherein thenatural extract is a botanical extract.
 17. The composition of claim 1,wherein the extract is selected from the group consisting of botanicalextracts, vegetal extracts, protein extracts, lipid extracts, marineextracts, algae extracts, milk extracts.
 18. The composition of claim 1,further comprising 1,3-propanediol.
 19. The composition of claim 18,wherein the 1,3-propanediol has at least 95% biobased carbon.
 20. Thecomposition of claim 19, wherein the 1,3-propanediol has 100% biobasedcarbon.
 21. A composition comprising 1,3-propanediol and an extractionproduct, wherein the 1,3-propanediol is biologically derived, whereinthe composition is biodegradable and has a lower anthropogenic CO₂emission profile as compared to a biodegradable composition comprising1,3-propanediol with a bio-based carbon content of 0%, and wherein the1,3-propanediol is a monomer, and comprises at least 3% biobased carbon.22. The composition of claim 21, wherein the 1,3-propanediol has atleast 85% biobased carbon.
 23. The composition of claim 21, wherein the1,3-propanediol has at least 95% biobased carbon.
 24. The composition ofclaim 21, wherein the 1,3-propanediol has 100% biobased carbon.
 25. Thecomposition of claim 21, wherein the extraction product is a naturalextract.
 26. The composition of claim 25, wherein the natural extract isa botanical extract.
 27. The composition of claim 21, wherein theextract is selected from the group consisting of botanical extracts,vegetal extracts, protein extracts, marine extracts, algae extracts,milk extracts.